The invention relates to the field of polyaspartic ester mixtures, and more particularly to the use of polyaspartic ester mixtures in polyurea coating applications.
Two-component polyurea coating compositions containing a polyisocyanate in combination with a polyaspartic ester component are known. They are suitable for the formation of coatings and can be adjusted to produce coatings that are hard, elastic, abrasion resistant, solvent resistant, and especially weather resistant. Despite their wide-spread use, however, known coating compositions contain disadvantages which limit their use in important applications.
Coating compositions with an appreciable amount of polyaspartic esters with dimethyl groups would be desired because dimethyl groups would add desired properties to coatings made from such compositions. U.S. Pat. No. 5,126,170 discloses a process for making polyurethane coatings in which an isocyanate-reactive component b) includes a polyaspartic ester mixture made from an optionally-substituted maleic or fumaric acid ester and a primary amine. Although the patent teaches that maleic acid or fumaric acid ester can be substituted with dimethyl, diethyl and di-n-butyl esters, it has been observed that during the Michael Addition Reaction of dimethyl maleate and primary amines, dimethyl maleate isomerizes to dimethyl fumarate in the presence of amines, according to the following geometric isomerization reaction: 
The dimethyl fumarate forms long needle-like crystals which no longer participate in the Michael Addition Reaction and prevent the reaction from completing. Although the resulting reaction produces yields of only about 30 to 40%, the entire composition is useless for commercial purposes. This is because the composition contains a mixture of compounds that preclude the formation of a suitable coating. The crude mixture generally contains (i) dimethyl fumarate crystals, (ii) starting diamine material, (iii) mono-primary-amine-monoaspartate and (iv) diaspartate. The presence of crystals in such a mixture prevents the formation of a coating. Filtering the crystals from the mixture has not been an option because filtration removes an appreciable amount of starting material, thereby adding substantial costs. Also, a filtrated mixture contains unreacted primary amines whose presence undesirably speed the crosslinking reaction.
U.S. Pat. No. 5,126,170 teaches preparing its polyaspartic esters in a solvent. The use of a 50% methanol reaction medium, however, is not practical in a production situation for the following reasons. First, the use of a 50% solution means that yields of product are half of what could be achieved if the reaction was run without solvent. Second, the methanol is highly flammable and its presence in manufacturing would be a safety hazard. Finally, in order for the polyaspartic ester to be used with polyisocyanates, the methanol would have to be completely removed. Even small, residual amounts of methanol would react with polyisocyanates to form urethanes, which would decrease the crosslink density of the films and so cause a decrease in properties.
For the foregoing reasons, it has been desired to develop a method for making a polyurea coating ingredient that contains an appreciable amount of dimethyl-substituted polyaspartic esters.
The invention relates to a method for making an asymmetric polyaspartic ester mixture by sequentially (a) forming an ester mixture containing a dimethyl-substituted first ester component and a second ester component substituted with an alkyl group having at least two carbon atoms and (b) reacting the ester component with an amine component, such that the equivalent number ratio of the first ester component and the second ester component is sufficient to prevent the formation of a reaction-stopping crude mixture containing dimethyl fumarate crystals.
The invention also relates to a polyurea coating composition containing a polyisocyanate component, the ester component used to make the polyaspartic ester mixture, and the asymmetric polyaspartic ester mixture, a method for making a coating with the polyaspartic ester mixture, and a coating made with the asymmetric polyaspartic ester mixture. These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
As used in this application, the term xe2x80x9ccyclic aminexe2x80x9d refers to amines which have at least one primary amine group attached to a cyclic (closed ring) group, e.g., an amine attached to a secondary ring carbon. The term xe2x80x9cacyclic aminexe2x80x9d refers to an amine that does not have a primary amine group attached to a cyclic, closed end group.
The invention is based on the surprising discovery that the crystallization that has been observed during the reaction of dimethyl-substituted maleic acid or dimethyl-substituted fumaric acid and a primary amine can be substantially reduced or eliminated altogether by reacting the amine with a mixture containing dimethyl maleate and a small amount of at least one dialkyl maleate having two or more carbon atoms, e.g., diethyl maleate, dipropyl maleate. By practicing the invention, polyaspartic esters based on dimethyl maleate can now be made simply and directly, without crystallization and without the need for solvents. The asymmetric polyaspartic ester mixtures produced can then be used as isocyanate-reactive components in coating compositions for making polyurea coatings having a novel structure and improved properties.
Maleic acid esters and fumaric acid esters include suitable dialkyl maleates or dialkyl fumarates. Suitable dialkyl maleates include dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, methyl propyl maleate, ethyl propyl maleate, and the like. Suitable dialkyl fumurates include dimethyl fumurate, diethyl fumurate, dipropyl fumurate, dibutyl fumurate, methyl propyl fumurate, ethyl propyl fumurate, and the like.
The amine component is generally selected from difunctional or trifunctional cyclic and acylic amines which can accomplish the objects of the invention. Suitable amines can be selected from the following. Suitable acyclic difunctional amines include but are not limited to ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4- and/or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and/or 2,6-hexahydrotolylenediamine, 2,4xe2x80x2- and/or 4,4xe2x80x2-diaminodicyclohexylmethane, and 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diaminodicyclohexylmethane. Suitable cyclic amines include aromatic polyamines such as 2,4- and/or 2,6-diaminotoluene, and 2,4xe2x80x2- and/or 4,4xe2x80x2-diaminodi-phenyl-methane are also suitable but less preferred. Other suitable cyclic amines include bis-(3-methyl-4-aminocyclohexyl) methane, 2,4-diamino-1-methyl, cyclohexane, and 2,6-diamino-1-methyl cyclohexane.
Suitable trifunctional amines include 4-aminomethyl-1,8-diamino-octane (also known as triaminononane supplied by Monsanto Company), tris-(2-aminoethyl)amine. It is believed that tetrafunctional amines, e.g., N,N,Nxe2x80x2,Nxe2x80x2-tetrakis-(2-aminoethyl)-1,2-ethanediamine are also suitable.
The equivalent number ratio of (i) the dimethyl maleates (or the dimethyl fumurates) to (ii) the dialkyl maleates (dialkyl fumurates) that have at least 2 carbon atoms is sufficient to prevent the formation of a reaction-stopping crude mixture containing dimethyl fumarate crystals. It has been discovered that cyclic amines containing substituted functional groups adjacent to a cyclically-bound amine group exhibit different behavior than acyclic amines and cyclic amines containing substituted groups that are not adjacent to a cyclically-bound amine group. As such, the following ranges are critical.
When a cyclic amine containing a substituted functional group adjacent to a cyclically-bound amine group is used, the equivalent number ratio is from less than 5:5 to more than 0:10, preferably from about 4.5:5.5 to 1:9, and even more preferably from about 4:6 to about 2:8. Stated in a number percentage basis, the amount of the dimethyl-substituted maleic acid ester or fumaric acid ester is present from less than 50% to more than 0%, preferably from about 45% to about 10%, and even more preferably from about 40 to about 20%, based on the total number of esters. Examples of such amines containing substituted groups adjacent to cyclically-bound amine groups include bis-(3-methyl-4-aminocyclohexyl) methane, 2,4-diamino-1-methyl, cyclohexane, and 2,6-diamino-1-methyl cyclohexane.
When an acyclic amine or a cyclic amine with or without a substituted group that is not adjacent to a cyclically-bound amine group is used, the equivalent number ratio is from less than 9:1 to more than 0:10, preferably from 8.5:1.5 to 1:9, and even more preferably 8:2 to 5.5. Stated in a number percentage basis, the amount of the dimethyl-substituted maleic acid ester or fumaric acid ester is present from less than 90% to more than 0%, preferably from about 85% to about 10%, and even more preferably from about 80 to about 50%, based on the total number of esters. The equivalent number ratio of the amine component to the ester component is generally about 1:1. As such, the ratio of the first ester component and the second ester component must be greater than 0:10. That is, the first ester component must be present in an amount that is greater than 0%, based on the total number of esters in the ester component.
The polyisocyanate component used to react with the polyaspartic ester mixtures includes any polyisocyanate, which, when used in accordance with the invention, meets the object of the invention. Suitable polyisocyanates for use as polyisocyanate component in accordance with the present invention include the known polyisocyanates of polyurethane chemistry. Examples of suitable low molecular weight polyisocyanates having a molecular weight of 168 to 300 include 1,4-diisocyanatobutane, 1,6-hexamethylene diisocyanate, 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyana-tomethylcyclohexane (IPDI), 2,4xe2x80x2- and/or 4,4xe2x80x2-diisocyanato-dicyclohexyl methane, 2,4- and/or 4,4xe2x80x2-diisocyanatodiphenyl methane and mixtures of these isomers with their higher homologues which are obtained in a known manner by the phosgenation of aniline/formaldehyde condenses, 2,4- and/or 2,6-diisocyanatotoluene and any mixtures of these compounds. Preferred cyclic is ocyanates include diphenylmethane 4,4xe2x80x2-diisocyanate (MDI), diphenylmethane 2,4xe2x80x2-diisocyanate, 2,4- and/or 2,6-diisocyanatotoluene. Preferred aliphatic isocyanates include hexamethylene diisocyanate, isophorone diisocyanate, 2,4xe2x80x2- and/or 4,4xe2x80x2-diisocyanato-dicyclohexyl methane.
Additional suitable polyisocyanate components include derivatives of the above-mentioned monomeric polyisocyanates, as is conventional in coatings technology. These derivatives include polyisocyanates containing biuret groups as described, for example, in U.S. Pat. Nos. 3,124,605 and 3,201,372 and DE-OS 1,101,394, incorporated herein by reference in their entirety; polyisocyanates containing isocyanurate groups as described in U.S. Pat. No. 3,001,973, DE-PS 1,022,789, 1,222,067 and 1,027,394 and DE-OS 1,929,034 and 2,004,048, incorporated herein by reference in their entirety; polyisocyanates containing urethane groups as described, for instance, in DE-OS 953,012, BE-PS 752,261 and U.S. Pat. Nos. 3,394,164 and 3,644,457; polyisocyanates containing carbodiimide groups as described in DE-PS 1,092,007, U.S. Pat. No. 3,152,162 and DE-OS 2,504,400, 2,537,685 and 2,552,350, incorporated herein by reference in their entirety; and polyisocyanates containing allophanate groups as described, for example, in GB-PS 994,890, BE-PS 761,626 and NL-OS 7,102,524. Suitable polyisocyanates also include polyisocyanates that contain uretdione groups. In one embodiment, asymmetric trimers such as those in U.S. Pat. No. 5,717,091, incorporated herein by reference in its entirety, can be used.
Isocyanate group-containing prepolymers and semi-prepolymers based on polyisocyanates can also be used as the polyisocyanate component. These prepolymers and semi-prepolymers generally have an isocyanate content ranging from about 0.5 to 30% by weight, preferably about 1 to 20% by weight, and are prepared in a known manner by the reaction of starting materials, e.g., isocyanate-reactive compounds such as polyols, at an NCO/OH equivalent number ratio of about 1.05:1 to 10:1, preferably about 1.1:1 to 3:1.
The asymmetric polyaspartic ester mixtures of the invention are made by combining a suitable polyamine component with an ester component containing maleic acid/fumaric acid mixture containing a dimethyl-substituted maleic acid/fumaric acid ester and a maleic acid/fumaric acid ester substituted with an alkyl group containing at least two carbon atoms in suitable amounts under conditions that favor the reaction of the reactants.
The duration of the reaction varies. Reactions involving aliphatic diamines such as hexane-diamine and 2-methyl-1,5-pentanediamine can be fully completed within two weeks. Reactions involving cyclic diamines such as H12MDI and 4xe2x80x2-dimethyl H12MDI ordinarily take a few months, e.g., 2-3 months, depending on the cyclic amine used when the reaction has reached 97 or 98% completion. Since it can take as long as 52 to 100 weeks for the reaction to reach 100% completion, it is ordinarily not practical to wait for full completion. Specific duration times can be obtained by routine experimentation. The yields at which the polyaspartic esters are produced are generally at least at about 70, 80 and preferably about 100%. The method is ordinarily practiced without any appreciable amount of an organic solvent, e.g., generally less than about 10% preferably less than 5%, based on the total weight of the solution, and even more preferably no solvents.
Generally, when difunctional amines are used, the asymmetric polyaspartic ester mixture includes, in addition to pure compounds, a polyaspartic ester having the formula: 
in which X is a hydrocarbon group obtained by the removal of amino groups from a amine corresponding to the formula, Xxe2x80x94(NH2)n in which R1 and R2 each are the same or different and each is an alkyl group having at least two carbon atoms and n is two. When trifunctional amines are used, the composition includes, in addition to pure compounds, one or both of the following polyaspartic esters: 
in which X is a hydrocarbon group obtained by the removal of amino groups from an amine corresponding to the formula Xxe2x80x94(NH2)n in which R1 and R2 each are the same or different and each is an alkyl group having at least two carbon atoms and n is three.
The method provides previously unavailable advantages. Since the method avoids the crystallization that ordinarily forms when dimethyl-substituted esters or maleic or fumaric acid reacts with amines, the method avoids the formation of a commercially useless reaction-stopping crude mixture containing dimethyl fumarate crystals (and other compounds) typically formed by known methods. Also, since the method of the invention does not require the use of solvents, e.g., methanol, it produces polyaspartic ester mixtures in greater yields than solvent-based systems, and avoids the fire hazards typically associated with flammable solvents. Also, since the method does not use solvents such as methanol, the crosslink density and properties of the films are not adversely affected by the polyurethanes which form by the reaction of residual amounts of methanol would react with polyisocyanates to form urethanes.
A polyurea coating composition can readily be formed by combining suitable amounts of (a) a polyisocyanate component and (b) an effective coating-forming amount of the asymmetric polyaspartic ester mixture. A coating is made from such a coating composition by (a) coating a substrate with a coating composition including effective coating-forming amounts of (i) a polyisocyanate component, and (ii) the asymmetric polyaspartic ester mixture. The polyisocyanate component and the asymmetric polyaspartic ester component are mixed in a ratio that is generally at least 0.9:1.1, preferably about 1:1 eq:eq, preferably from about 0.9:1.0 eq:eq to 1.5:1.0 and more preferably from about 0.9:1.0 eq:eq to 1.1:1 eq:eq. After the coating compositions have been applied to a suitable substrate, the compositions are hardened by curing at a suitable temperature, e.g., from about 30xc2x0 C. to 150xc2x0 C. In one embodiment, the polyisocyanate component and the effective coating-forming amounts of the asymmetric polyaspartic ester mixture also reacts with a polyol. Suitable polyols include polyols, e.g., polyethers such as those in U.S. Pat. No. 5,126,170, incorporated herein by reference in its entirety.
The coating can be made on substrates such as, cement, asphalt, metal, glass, and wood. The coatings are particularly useful in applications such as spray elastomer, heavy duty maintenance, product finishing, automotive, and flooring applications.